CN113603379B

CN113603379B - Ceramic composite material, shell, preparation method of shell and electronic equipment

Info

Publication number: CN113603379B
Application number: CN202110878508.1A
Authority: CN
Inventors: 胡梦; 陈奕君; 李聪
Original assignee: Guangdong Oppo Mobile Telecommunications Corp Ltd
Current assignee: Guangdong Oppo Mobile Telecommunications Corp Ltd
Priority date: 2021-07-30
Filing date: 2021-07-30
Publication date: 2023-08-08
Anticipated expiration: 2041-07-30
Also published as: CN113603379A

Abstract

The application provides a ceramic composite material, the ceramic composite material includes a plurality of ceramic microballoons, ceramic microballoons include waterborne resin layer and a plurality of first ceramic granule, waterborne resin layer parcel a plurality of first ceramic granule, the quality content of first ceramic granule is greater than 92% among the ceramic microballoons. The ceramic composite material has high ceramic phase content, can be used for preparing ceramic parts, and is beneficial to improving the ceramic phase content of the ceramic parts and improving the mechanical properties and ceramic texture of the ceramic parts. The application also provides a preparation method of the ceramic composite material, a shell, a preparation method of the shell and electronic equipment.

Description

Ceramic composite material, shell, preparation method of shell and electronic equipment

Technical Field

The application belongs to the technical field of electronic products, and particularly relates to a ceramic composite material, a shell, a preparation method of the ceramic composite material and electronic equipment.

Background

With the increase of the consumption level, consumers are not only pursuing diversification of functions, but also increasingly demanding the appearance, texture, etc. of electronic products. In recent years, ceramic materials have been a hot spot in research into electronic device housings because of their moist texture. In the related art, a product is prepared by a composite material formed by resin and a ceramic material, but compared with a real ceramic product, the product has larger difference in hardness, luster and warm hand feeling, and is difficult to obtain the real ceramic texture. Thus, there is still a need for improvements in ceramic housings and methods for their preparation.

Disclosure of Invention

In view of the above, the present application provides a ceramic composite material and a preparation method thereof, a housing and a preparation method thereof, and an electronic device.

In a first aspect, the present application provides a ceramic composite comprising a plurality of ceramic microspheres, the ceramic microspheres comprising an aqueous resin layer and a plurality of first ceramic particles, the aqueous resin layer encapsulating the plurality of first ceramic particles, the mass content of the first ceramic particles in the ceramic microspheres being greater than 92%.

In a second aspect, the present application provides a housing comprising a resin ceramic layer comprising a plurality of first ceramic particles, a plurality of second ceramic particles, a thermoplastic resin, and an aqueous resin, the first ceramic particles and the second ceramic particles being dispersed in a network formed by crosslinking the thermoplastic resin and the aqueous resin.

In a third aspect, the present application provides an electronic device comprising the housing of the second aspect.

In a fourth aspect, the present application provides a method for preparing a ceramic composite material, comprising: mixing and sanding the first ceramic particles, an aqueous initiator, a reactive surfactant and a binder to obtain mixed slurry, wherein the binder comprises at least one of aqueous resin and aqueous prepolymer; and spraying and granulating the mixed slurry to obtain a ceramic composite material, wherein the ceramic composite material comprises a plurality of ceramic microspheres, and the mass content of the first ceramic particles in the ceramic microspheres is more than 92%.

In a fifth aspect, the present application provides a method for manufacturing a shell, including: mixing and sanding the first ceramic particles, an aqueous initiator, a reactive surfactant and a binder to obtain mixed slurry, wherein the binder comprises at least one of aqueous resin and aqueous prepolymer; the mixed slurry is subjected to spray granulation to obtain a ceramic composite material, wherein the ceramic composite material comprises a plurality of ceramic microspheres, and the mass content of the first ceramic particles in the ceramic microspheres is more than 92%; blending the ceramic composite, the second ceramic particles, and a thermoplastic resin to form a blend; the blend is subjected to banburying granulation to form injection molding feeding, and the injection molding feeding is subjected to injection molding to obtain a resin ceramic blank; and pressing and heat treating the resin ceramic blank to obtain a resin ceramic layer, and thus obtaining the shell.

The ceramic composite material has high ceramic phase content, can be used for preparing ceramic parts, and is beneficial to improving the ceramic phase content of the ceramic parts; the preparation method of the ceramic composite material is simple, a large number of ceramic composite materials can be prepared, the mechanical property and ceramic texture of ceramic parts are improved, and the ceramic composite material is beneficial to application; the application also provides the shell and the preparation method thereof, and the shell is prepared by adopting the ceramic composite material, so that the content of a ceramic phase in the shell is improved, and the mechanical property and ceramic texture of the shell are improved; the electronic equipment with the shell has excellent mechanical properties, has strong ceramic texture and can meet the requirements of users.

Drawings

In order to more clearly describe the technical solutions in the embodiments of the present application, the drawings that are required to be used in the embodiments of the present application will be described below.

Fig. 1 is a schematic structural diagram of a ceramic composite material according to an embodiment of the present application.

Fig. 2 is a schematic structural diagram of a ceramic microsphere according to an embodiment of the present application.

Fig. 3 is a flowchart of a method for preparing a ceramic composite according to an embodiment of the present application.

Fig. 4 is a flowchart illustrating an operation of S101 in fig. 2 according to an embodiment of the present application.

Fig. 5 is a schematic process diagram of S102 according to an embodiment of the present application.

Fig. 6 is a schematic structural diagram of a housing according to an embodiment of the present disclosure.

Fig. 7 is a schematic structural diagram of a housing according to another embodiment of the present application.

Fig. 8 is a flowchart of a method for manufacturing a housing according to an embodiment of the present disclosure.

Fig. 9 is a schematic process diagram of S205 according to an embodiment of the present application.

Fig. 10 is a schematic structural diagram of an electronic device according to an embodiment of the present application.

Detailed Description

The following are preferred embodiments of the present application and it should be noted that modifications and adaptations to those skilled in the art may be made without departing from the principles of the present application and are intended to be within the scope of the present application.

The following disclosure provides many different embodiments or examples for implementing different structures of the present application. In order to simplify the disclosure of the present application, the components and arrangements of specific examples are described below. Of course, they are merely examples and are not intended to limit the present application. Furthermore, the present application may repeat reference numerals and/or letters in the various examples, which are for the purpose of brevity and clarity, and which do not in themselves indicate the relationship between the various embodiments and/or arrangements discussed. In addition, the present application provides examples of various specific processes and materials, but one of ordinary skill in the art may recognize the application of other processes and/or the use of other materials.

Referring to fig. 1, a schematic structural diagram of a ceramic composite material according to an embodiment of the present application is provided, wherein the ceramic composite material includes a plurality of ceramic microspheres 10; referring to fig. 2, a schematic structural diagram of a ceramic microsphere according to an embodiment of the present application is shown, wherein the ceramic microsphere 10 includes an aqueous resin layer 11 and a plurality of first ceramic particles 12, the aqueous resin layer 11 wraps the plurality of first ceramic particles 12, and a mass content of the first ceramic particles 12 in the ceramic microsphere 10 is greater than 92%. The ceramic microsphere 10 provided by the application has high ceramic phase content, can be used for preparing ceramic parts, and improves the mechanical properties and ceramic texture of the ceramic parts.

Referring to fig. 2, it can be understood that the aqueous resin layer 11 in the ceramic microsphere 10 is not a layer structure, and the aqueous resin layer 11 can be regarded as a "solvent", the first ceramic particles 12 can be regarded as a "solute", and the plurality of first ceramic particles 12 are dispersed in the aqueous resin layer 11 and are encapsulated by the aqueous resin layer 11.

In the ceramic composite material, the shape of the ceramic microspheres 10 may be, but not limited to, spheres, spheroids, etc., the shape and particle size may be the same or different among different ceramic microspheres 10, and the number of the first ceramic particles 12 contained in different ceramic microspheres 10 may be the same or different. It will be understood that the shape of the ceramic microspheres 10 and the number of first ceramic particles 12 contained in the ceramic microspheres 10 shown in fig. 1 and 2 of the present application are merely examples and are not limiting.

In the present embodiment, the aqueous resin layer 11 includes an aqueous resin, and the aqueous resin is crosslinked to form a three-dimensional network structure. In the present application, the aqueous resin layer 11 is a three-dimensional network structure formed by crosslinking of an aqueous resin, so that the first ceramic particles 12 can be dispersed in and wrapped by the three-dimensional network structure.

In the present embodiment, the aqueous resin layer 11 is formed by crosslinking at least one of an aqueous resin and an aqueous prepolymer by an aqueous initiator and a reactive surfactant. Under the action of the aqueous initiator and the reactive surfactant, the aqueous resin and/or the aqueous prepolymer may undergo a crosslinking reaction, thereby generating a three-dimensional network structure, forming the aqueous resin layer 11.

In the present application, the materials of the aqueous resin and the aqueous prepolymer may be selected as required, and are not limited thereto. In one embodiment of the present application, the aqueous resin includes at least one of an aqueous acrylic resin, an aqueous polyurethane resin, and an aqueous epoxy resin. The adoption of the water-based resin is beneficial to forming a three-dimensional network structure with good toughness and compactness, and improves the performance of the water-based resin layer 11. In one embodiment of the present application, the aqueous prepolymer includes at least one of an aqueous acrylic prepolymer, an aqueous polyurethane prepolymer, and an aqueous epoxy prepolymer. The adoption of the prepolymer is favorable for generating a cross-linking reaction to generate a three-dimensional network structure with good toughness and compactness, and improves the performance of the water-based resin layer 11. Further, the molecular weight of the aqueous prepolymer is 3000-8000, which is beneficial to improving the elasticity of the ceramic microsphere 10.

In this application, an aqueous initiator is used to initiate the polymerization reaction. In embodiments of the present application, the aqueous initiator includes an aqueous peroxide, and in particular, the aqueous peroxide may include, but is not limited to, at least one of ammonium persulfate and potassium persulfate. In the present application, the reactive surfactant means a surfactant having a reactive group, which is capable of chemically reacting with an aqueous resin or an aqueous prepolymer. In the present embodiment, the reactive surfactant may have at least one of an epoxy group, an olefin group, and a maleic anhydride diester group, but is not limited thereto. Specifically, the reactive surfactant may include, but is not limited to, at least one of an alkylene oxide-based reactive surfactant, a maleic acid diester-based reactive surfactant, and the like.

In the present embodiment, the first ceramic particles 12 comprise Al ₂ O ₃ 、ZrO ₂ 、Si ₃ N ₄ 、SiO ₂ 、TiO ₂ At least one of AlN, siC and Si. The first ceramic particles 12 are high-temperature resistant, corrosion resistant, high in hardness and good in strength, and are beneficial to improving the mechanical properties of ceramic parts. In one embodiment of the present application, the refractive index of the first ceramic particles 12 is greater than 2, which is advantageous for improving the ceramic texture and gloss of the ceramic part. In the present embodiment, the particle diameter D50 of the first ceramic particles 12 is 80nm to 5 μm. The choice of the first ceramic particles 12 of the above-mentioned particle size facilitates the preparation of ceramic composite materials with a high ceramic phase content. In one embodiment of the present application, the first ceramic particles 12 have a particle size D50 of 80nm to 300nm. The first ceramic particles 12 having the above particle size are advantageous for the preparation of a ceramic composite material having a high ceramic phase content, and for the dispersion of the first ceramic particles 12 in the aqueous resin layer 11. Specifically, the particle diameter D50 of the first ceramic particles 12 may be, but is not limited to, 80nm, 100nm, 130nm, 150nm, 190nm, 200nm, 240nm, 250nm, 260nm, 280nm, 290nm, or the like.

In the application, the mass content of the first ceramic particles 12 in the ceramic microsphere 10 is more than 92%, so that the ceramic composite material has high solid content, can be used in the preparation of ceramic pieces, and improves the ceramic phase content of the ceramic pieces. Further, the ceramic microspheres 10 have a mass content of the first ceramic particles 12 of more than 93%. Further, the ceramic microspheres 10 have a mass content of the first ceramic particles 12 of greater than 95%. In the present application, one ceramic microsphere 10 contains a plurality of first ceramic particles 12, and the plurality of first ceramic particles 12 are surrounded by an aqueous resin layer 11. In the present embodiment, the particle size of the ceramic microspheres 10 is in the order of micrometers. Further, the particle diameter D50 of the ceramic microspheres 10 is 20 μm to 50. Mu.m. Further, the particle diameter D50 of the ceramic microspheres 10 is 30 μm to 40. Mu.m. Specifically, the particle diameter D50 of the ceramic microspheres 10 may be, but is not limited to, 20 μm, 25 μm, 30 μm, 32 μm, 40 μm, 46 μm, 50 μm, or the like. In the present application, the shape of the ceramic microspheres 10 may be, but not limited to, spheres, spheroids, and the like, and is not limited thereto.

Referring to fig. 3, a flowchart of a method for preparing a ceramic composite according to an embodiment of the present application includes:

s101: mixing the first ceramic particles, an aqueous initiator, a reactive surfactant and a binder, and sanding to obtain mixed slurry, wherein the binder comprises at least one of aqueous resin and aqueous prepolymer.

S102: and (3) spraying and granulating the mixed slurry to obtain the ceramic composite material, wherein the ceramic composite material comprises a plurality of ceramic microspheres, and the mass content of the first ceramic particles in the ceramic microspheres is more than 92%.

In S101, a mixed slurry is formed by mixing the first ceramic particles 12, the aqueous initiator, the reactive surfactant, and the binder, and sanding. In this application, the above materials are uniformly mixed and the reactive surfactant and binder are coated on the surface of the first ceramic particles 12 in sanding, facilitating the subsequent spray granulation and the preparation of the ceramic composite.

In the present application, the aqueous resin and/or the aqueous prepolymer have a certain adhesion effect, and after the aqueous resin and/or the aqueous prepolymer wraps the aqueous initiator and the reactive surfactant in the spray granulation process of the mixed slurry, the aqueous resin and/or the aqueous prepolymer are wrapped on the surface of the first ceramic particles 12 together, and under the effect of the aqueous initiator, the aqueous resin and/or the aqueous prepolymer and the aqueous resin and/or the aqueous prepolymer react with each other to form a more compact three-dimensional network structure, so that the plurality of first ceramic particles 12 are tightly adhered together, thereby being beneficial to the preparation of the ceramic microspheres 10 with high ceramic phase content. In the present embodiment, the aqueous resin includes at least one of an aqueous acrylic resin, an aqueous urethane resin, and an aqueous epoxy resin. The aqueous resin may be a single-component aqueous resin, a two-component aqueous resin, or a mixture of both, and is not limited thereto. In embodiments of the present application, the aqueous prepolymer includes at least one of an aqueous acrylic prepolymer, an aqueous polyurethane prepolymer, and an aqueous epoxy prepolymer. Further, the molecular weight of the aqueous prepolymer is 3000-8000, which is beneficial to improving the elasticity of the ceramic microsphere 10, and simultaneously, the aqueous prepolymer is easier to crosslink with thermoplastic resin in the subsequent process, so as to form a more compact and high-toughness interface. It will be appreciated that the aqueous resin/aqueous prepolymer may be selected from other aqueous resins/aqueous prepolymers not listed above but having the same function.

In this application, reactive surfactants refer to surfactants with reactive groups that are capable of chemically reacting with the binder. In the present embodiment, the reactive surfactant may have at least one of an epoxy group, an olefin group, and a maleic anhydride diester group, but is not limited thereto. Specifically, the reactive surfactant may include, but is not limited to, at least one of an alkylene oxide-based reactive surfactant, a maleic acid diester-based reactive surfactant, and the like. In the present embodiment, the mass of the reactive surfactant is 0.5% -2% of the mass of the first ceramic particles 12. Further, the mass of the reactive surfactant is 1% -1.5% of the mass of the first ceramic particles 12. Specifically, the mass of the reactive surfactant may be, but is not limited to, 0.5%, 0.8%, 1%, 1.3%, 1.6%, 1.8%, 2% or the like of the mass of the first ceramic particles 12. The use of the reactive surfactant at the levels described above facilitates the reaction of the first ceramic particles 12 with the binder to promote the formation of a tight crosslinked network.

In this application, an aqueous initiator is used to initiate the polymerization reaction, and by using an aqueous initiator, uniform mixing between the substances in the mixed slurry is facilitated. In one embodiment, the aqueous initiator comprises an aqueous peroxide, which may include, but is not limited to, at least one of ammonium persulfate and potassium persulfate. In embodiments of the present application, the mass of the aqueous initiator is 1% -3% of the mass of the reactive surfactant. Further, the mass of the aqueous initiator accounts for 1.5% -2.5% of the mass of the reactive surfactant. Specifically, the mass of the aqueous initiator may be, but is not limited to, 1.6%, 2%, 2.2%, 2.8%, 3% or the like of the mass of the reactive surfactant. The adoption of the water-based initiator with the content is favorable for the reaction between the binders and the reactive surfactant to form a compact crosslinking interface.

In an embodiment of the present application, the first ceramic particles 12, the aqueous initiator, the reactive surfactant, and the binder further comprise sanding the first ceramic particles 12 to obtain the desired morphology, particle size of the first ceramic particles 12. In the embodiment of the application, the sanding rotational speed is 500r/min-2000r/min, the particle size of the sanding beads is 0.3mm-10mm, and the sanding time is 2h-16h, so that the appearance and the particle size of the first ceramic particles 12 can be improved. Further, the sanding rotational speed is 800r/min-1700r/min, the particle size of the sand beads is 1mm-8mm, and the sanding time is 4h-12h. In one embodiment, the first ceramic particles 12 are mixed with sanding beads for sanding. In another embodiment, the first ceramic particles 12, dispersant and sanding beads are placed in a solvent and sanded, and dried after sanding. Wherein the dispersing agent can be at least one of sodium dodecyl sulfonate, sodium hexametaphosphate, sodium benzoate and polyvinyl alcohol, and the solvent can be water, alcohol solvent or alcohol-water solvent. Further, the first ceramic particles 12 are obtained by flash evaporation. Specifically, the flash vaporization temperature may be, but is not limited to, 100℃to 280℃and the flash vaporization rate is 2kg/h to 5kg/h. In one embodiment, the first ceramic particles 12 having a particle diameter D50 of 80nm to 5 μm can be obtained by the above-described sanding treatment.

Referring to fig. 4, a flowchart of the operation of S101 in fig. 3 according to an embodiment of the present application includes:

s1011: the binder is dissolved in water to form a binder solution.

S1012: the first ceramic particles, the aqueous initiator and the reactive surfactant are added to the binder solution to form a mixed solution.

S1013: and (5) sanding the mixed solution to obtain mixed slurry.

In S1011, the binder is dissolved in water to form a binder solution, and then the other substances are added to form a mixed solution. By adding various substances into the aqueous system, the mixed solution of the aqueous system is formed, which is beneficial to the mixing of the substances and the subsequent spray granulation. In one embodiment, the mass content of the binder in the binder solution is greater than or equal to 2%. Further, the mass content of the binder in the binder solution is 2% -8%. Specifically, the mass content of the binder in the binder solution may be, but is not limited to, 2%, 2.5%, 3%, 4%, 5%, 5.8%, 6%, 7% or 7.5%, etc.

In S1012, the first ceramic particles 12, the aqueous initiator, and the reactive surfactant are added to the binder solution to form a mixed solution. Specifically, the first ceramic particles 12, the aqueous initiator, and the reactive surfactant may be added at a rotational speed of 100r/min to 500r/min, but are not limited thereto, to improve the uniformity of dispersion of the components. In one embodiment, the reactive surfactant and the aqueous initiator may be added to the binder solution before the first ceramic particles 12 are added, which is advantageous in that the binder, the reactive surfactant and the aqueous initiator can uniformly encapsulate the first ceramic particles 12 during the sanding and spray granulation processes.

In the embodiment of the present application, the mass content of the first ceramic particles 12 in the mixed solution is 30% or more. Further, the mass content of the first ceramic particles 12 in the mixed solution is 30% -70%. Further, the mass content of the first ceramic particles 12 in the mixed solution is 45% -65%. Specifically, the mass content of the first ceramic particles 12 in the mixed solution may be, but is not limited to, 30%, 40%, 47%, 50%, 55%, 60%, 68%, or the like. The mixed solution with the content of the first ceramic particles 12 can ensure that all substances are uniformly mixed, and can ensure the high content of the first ceramic particles 12 at the same time, so that the preparation of the ceramic microspheres 10 with high solid content is facilitated.

In one embodiment of the present application, mixing the first ceramic particles 12, the aqueous initiator, the reactive surfactant, and the binder to form a mixed solution includes: dissolving a binder in water to form a binder solution, wherein the mass content of the binder in the binder solution is 2% -8%; the first ceramic particles 12, the aqueous initiator and the reactive surfactant are added into the binder solution to form a mixed solution, wherein the mass of the aqueous initiator accounts for 1-3% of the mass of the reactive surfactant, the mass of the reactive surfactant accounts for 0.5-2% of the mass of the first ceramic particles 12, and the mass of the first ceramic particles 12 accounts for 30-70% of the mass of the mixed solution. Not only is beneficial to the uniform dispersion of all substances, but also is beneficial to the subsequent spray granulation, and is beneficial to the preparation of the ceramic microspheres 10 with high solid content.

In S1013, the mixed solution is sanded, so that the reactive surfactant and the binder are wrapped on the surface of the first ceramic particles 12, thereby facilitating the cross-linking reaction in the subsequent spray granulation process and ensuring the formation of the ceramic microspheres 10 with high solid content. Specifically, the mixed liquor can be, but is not limited to, placed in a sand mill for sand milling. In an embodiment of the present application, the sanding of the mixed liquor comprises: the mixed solution is placed in a sanding system and circulated for 5-10 cycles at a sanding rotational speed of 800-1500 r/min, and one cycle time is 15-30 min. Specifically, the sanding rotation speed can be, but not limited to, 800r/min, 1000r/min, 1200r/min, 1300r/min, 1500r/min, etc., and one cycle time can be, but not limited to, 15min, 18min, 20min, 24min, 27min, 30min, etc. The sanding process is beneficial to uniformly wrapping the binder, the reactive surfactant and the aqueous initiator on the surface of the first ceramic particles 12 to form stable and uniformly dispersed slurry, and is beneficial to the formation of the ceramic microspheres 10.

In S102, the ceramic microsphere 10 with high ceramic content is obtained by spray granulating the mixed slurry, in the spray granulating process, droplets are formed by spraying, then granulating is performed to evaporate the solvent in the droplets and the binder on the surface of the first ceramic particle 12 is close to each other and wound into spheres, and at the same time, the granulating temperature is such that the binder and the reactive surfactant coated on the surface of the first ceramic particle 12 react under the action of the aqueous initiator, thereby forming a compact cross-linked network structure on the surface of the first ceramic particle 12, and forming the compact ceramic microsphere 10 with ceramic content of more than 92%. It will be appreciated that the ceramic microspheres 10 are formed to include a plurality of first ceramic particles 12, the plurality of first ceramic particles 12 being bound together by a binder. In embodiments of the present application, when the binder comprises an aqueous prepolymer, at least a portion of the aqueous prepolymer undergoes a crosslinking reaction during spray granulation to form the corresponding aqueous resin.

In the application, spray granulation comprises a spraying process and a granulating process, wherein the temperature of the spraying process is selected according to the property of a solvent in the mixed slurry, and the spraying temperature is smaller than the volatilization temperature of the solvent so as to ensure the formation of liquid drops; the granulation temperature is greater than the initiation temperature of the initiator and the volatilization temperature of the solvent in the mixed slurry, and is less than the thermal decomposition temperature of the binder and the reactive surfactant, thereby ensuring the reaction between the binder and the reactive surfactant, and better encapsulating the first ceramic particles 12 to produce ceramic microspheres 10. In one embodiment of the present application, the mixed slurry is prepared by sanding a mixed solution of an aqueous system, and the granulating temperature in the spray granulating process is greater than the volatilization temperature of the solvent of the aqueous system, thereby facilitating the formation of the granular ceramic microspheres 10. In one embodiment of the present application, the temperature of granulation is 150 ℃ to 280 ℃. Further, the granulating temperature is 170-250 ℃. Specifically, the temperature of the granulation may be, but not limited to, 150 ℃, 170 ℃, 180 ℃, 200 ℃, 230 ℃, 250 ℃, or the like.

In the embodiment of the present application, the ceramic microsphere 10 includes an aqueous resin layer 11 and a plurality of first ceramic particles 12, the aqueous resin layer 11 encapsulates the plurality of first ceramic particles 12, and the aqueous resin layer 11 is formed by crosslinking a binder under the action of an aqueous initiator and a reactive surfactant. In the preparation process, the aqueous resin and/or the aqueous prepolymer are mixed with the aqueous initiator and the reactive surfactant, and the first ceramic particles 12 are dispersed therein, and in the spray granulation process, the formed droplets are dried to obtain the ceramic microspheres 10, wherein a plurality of the first ceramic particles 12 are wrapped by a three-dimensional network structure formed by crosslinking the aqueous resin and/or the aqueous prepolymer.

Referring to fig. 5, a schematic process diagram of S102 is provided in an embodiment of the present application, in which a mixed slurry containing the first ceramic particles 12, an aqueous initiator, a reactive surfactant and a binder is spray granulated; droplets are formed during spraying; in the high-temperature granulation process, the solvent in the liquid drops volatilizes, the binder on the surfaces of the first ceramic particles 12 is mutually close to each other and is wound into spheres, and meanwhile, the binder wrapped on the surfaces of the first ceramic particles 12 and the reactive surfactant react under the action of the aqueous initiator, so that a compact cross-linked network structure is formed on the surfaces of the first ceramic particles 12, and the compact ceramic microsphere 10 with high solid content is prepared. It will be appreciated that fig. 2 and 5 each show a schematic view of the ceramic microsphere 10, wherein fig. 2 is a schematic view of a section of the ceramic microsphere 10 shown in a macroscopic view, and fig. 5 shows a microstructure of the aqueous resin layer 11 in the ceramic microsphere, that is, the aqueous resin layer 11 shows a three-dimensional network structure in a microscopic view, and the first ceramic particles 12 are wrapped by the three-dimensional network structure.

In the present application, the ceramic composite material in any one of the above embodiments may be prepared by the preparation method of the ceramic composite material provided in the present application.

Referring to fig. 6, a schematic structural diagram of a housing according to an embodiment of the present application is provided, the housing 100 includes a resin ceramic layer 20, the resin ceramic layer 20 includes a plurality of first ceramic particles 12, a plurality of second ceramic particles, a thermoplastic resin and an aqueous resin, and the first ceramic particles 12 and the second ceramic particles are dispersed in a network structure formed by crosslinking the thermoplastic resin and the aqueous resin. The shell 100 provided by the application has excellent mechanical property and strong ceramic texture, and has wide application prospect.

In the embodiment of the present application, the total mass content of the first ceramic particles 12 and the second ceramic particles in the resin ceramic layer 20 is 84% or more. The higher content of the first ceramic particles 12 and the second ceramic particles in the resin ceramic layer 20 can effectively improve the surface hardness of the housing 100, and simultaneously improve the ceramic texture of the housing 100. Further, the total mass content of the first ceramic particles 12 and the second ceramic particles in the resin ceramic layer 20 is 85% or more. Still further, the total mass content of the first ceramic particles 12 and the second ceramic particles in the resin ceramic layer 20 is 87% or more. The ceramic content in the shell 100 is high, and the mechanical property and ceramic texture of the shell 100 are improved.

In the present embodiment, the first ceramic particles 12 comprise Al ₂ O ₃ 、ZrO ₂ 、Si ₃ N ₄ 、SiO ₂ 、TiO ₂ At least one of AlN, siC and Si. The first ceramic particles 12 are high temperature resistant, corrosion resistant, high in hardness and high in strength, and are beneficial to improving the mechanical properties of the shell 100. In one embodiment of the present application, the refractive index of the first ceramic particles 12 is greater than 2, thereby advantageously improving the ceramic feel and gloss of the housing 100. In the present embodiment, the particle diameter D50 of the first ceramic particles 12 is 80nm to 5 μm. In one embodiment of the present application, the first ceramic particles 12 have a particle size D50 of 80nm to 300nm. Specifically, the particle diameter D50 of the first ceramic particles 12 may be, but is not limited to, 80nm, 100nm, 130nm, 150nm, 190nm, 200nm, 240nm, 250nm, 260nm, 280nm, 290nm, or the like.

In an embodiment of the present application, the second ceramic particles comprise Al ₂ O ₃ 、ZrO ₂ 、Si ₃ N ₄ 、SiO ₂ 、TiO ₂ At least one of AlN, siC and Si. The second ceramic particles are high-temperature resistant, corrosion resistant, high in hardness and good in strength, and are beneficial to improving the performance of the shell 100. In one embodiment of the present application, the refractive index of the second ceramic particles is greater than 2, thereby advantageously improving the ceramic texture and gloss of the housing 100. In an embodiment of the present application, the second ceramic particles have a particle size D50 of 80nm to 5 μm. Selection of The second ceramic particles of the above particle size contribute to the mechanical properties of the housing 100. Further, the second ceramic particles have a particle diameter D50 of 350nm to 4 μm. Further, the second ceramic particles have a particle diameter D50 of 1 μm to 3. Mu.m. Specifically, the particle diameter D50 of the second ceramic particles may be, but is not limited to, 500nm, 600nm, 900nm, 1 μm, 1.5 μm, 1.8 μm, 2.1 μm, 2.5 μm, 3 μm, 3.7 μm, 4.5 μm, or the like. In one embodiment of the present application, the first ceramic particles 12 have a smaller particle size than the second ceramic particles. The smaller particle size of the first ceramic particles 12 makes the ceramic microsphere 10 easier to prepare, while the larger particle size of the second ceramic particles can improve the mechanical properties of the housing 100. In the present application, the materials and the morphology of the first ceramic particles 12 and the second ceramic particles may be the same or different, and the present invention is not limited thereto.

In the present application, the resin in the resin ceramic layer 20 is crosslinked to form a network structure in which the first ceramic particles 12 and the second ceramic particles are dispersed, and the resin includes a thermoplastic resin and an aqueous resin. In the embodiment of the present application, the mass content of the resin in the resin ceramic layer 20 is 16% or less. Further, the mass content of the resin in the resin ceramic layer 20 is 15% or less. Further, the mass content of the resin in the resin ceramic layer 20 is 14% or less. The resin contained in the housing 100 can effectively reduce the quality of the housing 100, and meets the requirement of light and thin. In an embodiment of the present application, the thermoplastic resin includes at least one of polyphenylene sulfide, polycarbonate, polyamide, polybutylene terephthalate, and polymethyl methacrylate, and the aqueous resin includes at least one of aqueous acrylic resin, aqueous polyurethane resin, and aqueous epoxy resin. In one embodiment, the mass content of the thermoplastic resin in the resin is greater than or equal to 90%, so that the usability of the case 100 can be ensured.

In the embodiment, the resin ceramic layer 20 is made of ceramic microspheres 10, thermoplastic resin and second ceramic particles, the ceramic microspheres 10 comprise an aqueous resin layer 11 and a plurality of first ceramic particles 12, the aqueous resin layer 11 wraps the plurality of first ceramic particles 12, the mass content of the first ceramic particles 12 in the ceramic microspheres 10 is more than 92%, and the aqueous resin layer 11 comprises aqueous resin; after the ceramic microspheres 10 are broken, the aqueous resin and the thermoplastic resin are crosslinked to form a network structure, and the first ceramic particles 12 and the second ceramic particles are dispersed in the network structure to form a resin ceramic layer 20. That is, the ceramic microspheres 10, the thermoplastic resin, and the second ceramic particles are mixed during the preparation, and then the aqueous resin layer 11 of the ceramic microspheres 10 is broken so that the first ceramic particles 12 are in contact with the thermoplastic resin, and cross-linking occurs between the thermoplastic resin and the aqueous resin, resulting in a network structure in which the first ceramic particles 12 and the second ceramic particles are finally dispersed.

The hardness of the surface of the resin ceramic layer 20 was examined by using GB/T6739-1996 standard. In the embodiment of the present application, the pencil hardness of the surface of the resin ceramic layer 20 is 7H or more. Further, the pencil hardness of the surface of the resin ceramic layer 20 is 7H to 10H, thereby greatly improving the hardness and strength of the case 100. Further, the pencil hardness of the surface of the resin ceramic layer 20 is 7H to 9H. Specifically, the pencil hardness of the surface of the resin ceramic layer 20 may be, but not limited to, 7H, 8H, 9H, or the like.

In this application, the performance of the resin ceramic layer 20 was examined using a ball drop impact performance test, in which the ball drop was a stainless steel ball of 32g, and the thickness of the resin ceramic layer 20 was 0.8mm. In one embodiment, the resin ceramic layer 20 is supported on the jig, wherein the peripheral edge of the resin ceramic layer 20 has a 3mm support, and the middle part is suspended; the 32g stainless steel ball is freely dropped from a certain height to a to-be-detected point on the surface of the resin ceramic layer 20 to be detected, and the height for crushing the resin ceramic layer 20 is recorded as the falling height. Further, a stainless steel ball of 32g was freely dropped from a certain height to five detection points at four corners and the center of the surface of the resin ceramic layer 20 to be measured, and the height at which the resin ceramic layer 20 was broken was recorded as the drop height. In the embodiment of the present application, the ball drop height of the resin ceramic layer 20 is 50cm or more. Further, the ball drop height of the resin ceramic layer 20 is 55cm to 100cm. Further, the ball drop height of the resin ceramic layer 20 is 60cm to 90cm.

In the embodiment of the present application, the resin ceramic layer 20 has an angular glossiness of 20 ° of 160 or more, an angular glossiness of 60 ° of 130 or more, and an angular glossiness of 80 ° of 85 or more. Further, the resin ceramic layer 20 has an angular glossiness of 170 or more at 20 °, an angular glossiness of 152 or more at 60 °, and an angular glossiness of 90 or more at 80 °.

In the embodiment of the present application, the resin ceramic layer 20 may further have a colorant so that the case 100 has a different color appearance, improving visual effect. Specifically, the colorant may be, but is not limited to, at least one selected from the group consisting of iron oxide, cobalt oxide, cerium oxide, nickel oxide, bismuth oxide, zinc oxide, manganese oxide, chromium oxide, copper oxide, vanadium oxide, and tin oxide, respectively. In one embodiment, the mass content of colorant in the resin ceramic layer 20 is less than or equal to 10% so as to improve the color of the resin ceramic layer 20 without affecting the content of the first ceramic particles 12. Further, the mass content of the colorant in the resin ceramic layer 20 is 0.5% to 10%.

Referring to fig. 7, in order to provide a schematic structural diagram of a housing according to another embodiment of the present application, the housing 100 may further include a protection layer 30, where the protection layer 30 is disposed on a surface of the resin ceramic layer 20. The housing 100 has opposite inner and outer surfaces during use, and the protective layer 30 is located on one side of the outer surface to provide protection during use of the housing 100. Specifically, the protective layer 30 may be, but is not limited to, an anti-fingerprint layer, a hardened layer, or the like. Specifically, the thickness of the protective layer 30 may be, but is not limited to, 5nm to 20nm. In one embodiment, the protective layer 30 includes an anti-fingerprint layer. Optionally, the contact angle of the anti-fingerprint layer is greater than 105 °. The contact angle is an important parameter for measuring the wettability of the liquid on the surface of the material, and the contact angle of the anti-fingerprint layer is larger than 105 degrees, which indicates that the liquid can easily move on the anti-fingerprint layer, so that the pollution to the surface of the anti-fingerprint layer is avoided, and the anti-fingerprint material has excellent anti-fingerprint performance. Optionally, the anti-fingerprint layer comprises a fluorine-containing compound. In particular, the fluorine-containing compound may be, but is not limited to, fluorosilicone resin, perfluoropolyether, fluoroacrylate, and the like. Furthermore, the anti-fingerprint layer further comprises silicon dioxide, and the friction resistance of the anti-fingerprint layer is further improved by adding the silicon dioxide. In another embodiment, the protective layer 30 includes a hardened layer. The surface hardness of the case 100 is further enhanced by providing a hardened layer. Optionally, the material of the hardening layer comprises at least one of polyurethane acrylate, organic silicon resin and perfluoropolyether acrylate.

In the present application, the thickness of the housing 100 may be selected according to the requirements of the application scenario, which is not limited; in an embodiment, the housing 100 may be used as a casing, a middle frame, a decoration, etc. of the electronic device 200, such as a casing of a mobile phone, a tablet computer, a notebook computer, a watch, an MP3, an MP4, a GPS navigator, a digital camera, etc. The housing 100 in the embodiment of the present application may be a 2D structure, a 2.5D structure, a 3D structure, or the like, and may be specifically selected as needed. In one embodiment, the thickness of the housing 100 is 0.6mm-1.2mm when the housing 100 is used as a rear cover of a mobile phone. Specifically, the thickness of the housing 100 may be, but is not limited to, 0.6mm, 0.7mm, 0.8mm, 0.9mm, 1mm, 1.1mm, or 1.2mm. In another embodiment, when the housing 100 is used as a mobile phone rear cover, the housing 100 includes a main body portion and an extension portion disposed at an edge of the main body portion, and the extension portion is bent toward the main body portion; the housing 100 is curved at this time. In the present embodiment, the surface roughness of the case 100 is less than 0.1 μm. By providing the housing 100 with small surface roughness, the ceramic texture is enhanced, and the visual effect is improved. Further, the surface roughness of the case 100 is 0.02 μm to 0.08 μm.

Referring to fig. 8, a flowchart of a method for manufacturing a shell according to an embodiment of the present application includes:

s201: mixing the first ceramic particles, an aqueous initiator, a reactive surfactant and a binder, and sanding to obtain mixed slurry, wherein the binder comprises at least one of aqueous resin and aqueous prepolymer.

S202: and (3) spraying and granulating the mixed slurry to obtain the ceramic composite material, wherein the ceramic composite material comprises a plurality of ceramic microspheres, and the mass content of the first ceramic particles in the ceramic microspheres is more than 92%.

S203: the ceramic composite, the second ceramic particles, and the thermoplastic resin are blended to form a blend.

S204: and (3) carrying out banburying granulation on the blend to form an injection molding feed, and carrying out injection molding on the injection molding feed to obtain a resin ceramic blank.

S205: and pressing and heat treating the resin ceramic blank to obtain a resin ceramic layer, and thus obtaining the shell.

In the application, the ceramic microspheres 10 with the content of the first ceramic particles 12 being more than 92% are matched with the second ceramic particles and the thermoplastic resin, so that the ceramic phase content in the shell 100 is improved; meanwhile, the resin phase in the ceramic microspheres 10 is mutually reacted and fused with the thermoplastic resin, so that the interface strength is enhanced, and the mechanical property of the shell 100 is improved; the preparation method is simple and easy to operate, can realize industrial production, and is beneficial to the use of the shell 100. In the related art, when ceramic particles are directly matched with thermoplastic resin for preparing the shell 100, the content of the ceramic particles is improved to influence the fluidity of injection molding feeding, so that the mechanical property of the shell 100 is obviously reduced, even the shell 100 cannot be molded, and the production yield is influenced. In the application, the content of the first ceramic particles 12 in the ceramic microsphere 10 is high, which is favorable for the increase of the ceramic phase of the shell 100, and the resin phase in the ceramic microsphere 10 can be mutually reacted and wound together with the thermoplastic resin to form a compact bonding interface, so that the integral strength is improved, and meanwhile, the addition of the ceramic microsphere 10 can not influence the flow of injection molding feeding, so that the mechanical property of the shell 100 is improved while the ceramic phase in the shell 100 is increased.

It can be appreciated that, for the detailed description of S201 and S202, please refer to the description of the corresponding parts of S101 and S102 in the preparation method of the ceramic composite material, and the detailed description is omitted herein.

In S203, by adding the ceramic composite material with high ceramic phase content into the second ceramic particles and the thermoplastic resin, the content of the ceramic phase in the blend can be improved, and meanwhile, the fluidity of the subsequent injection molding feed can be ensured, and the mechanical property of the shell 100 can be ensured.

In the embodiment of the application, the mass content of the ceramic composite material in the blend is more than or equal to 60%, which is beneficial to improving the content of the ceramic phase in the shell 100 and enhancing the surface glossiness and ceramic texture of the shell 100. Further, the mass content of the ceramic composite material in the blend is greater than or equal to 70%. Further, the mass content of the ceramic composite material in the blend is greater than or equal to 80%. Specifically, the mass content of the ceramic composite in the blend may be, but is not limited to, 60%, 65%, 68%, 70%, 73%, 75%, 80%, 85%, 83%, 90%, or the like.

In embodiments of the present application, the mass ratio of the ceramic composite to the second ceramic particles in the blend is from 1.7 to 18. The ceramic composite material and the second ceramic particles are added to increase the content of the ceramic phase in the blend, and the melt index of the subsequent injection molding feeding can be ensured, so that the preparation yield of the shell 100 and the performance of the prepared shell 100 are ensured. Further, the mass ratio of the ceramic composite material to the second ceramic particles in the blend is 2.5-15. Still further, the mass ratio of the ceramic composite to the second ceramic particles in the blend is from 5 to 12. Specifically, the mass ratio of the ceramic composite to the second ceramic particles in the blend may be, but is not limited to, 2, 4, 6, 9, 10, 13, 15, 17, etc. In the present application, the first ceramic particles 12 and the second ceramic particles may be the same in material, morphology, and particle size, or may be different from each other, and are not limited thereto.

In the present application, the weight of the produced housing 100 is reduced by adding the thermoplastic resin, while allowing the housing 100 to have excellent toughness. In an embodiment of the present application, the thermoplastic resin includes at least one of polyphenylene sulfide, polycarbonate, polyamide, polybutylene terephthalate, and polymethyl methacrylate. The physical and chemical properties of the thermoplastic resin can be matched with the preparation process of the shell 100, so that the thermoplastic resin cannot be decomposed in the preparation process, the difficulty of the preparation process cannot be increased, and the production cost is reduced. It will be appreciated that other thermoplastic resins not listed above that are suitable for use in preparing the housing 100 may also be selected.

In one embodiment of the present application, the blend has a ceramic composite mass content of 60% to 90%, a second ceramic particle mass content of 5% to 33%, and a thermoplastic resin mass content of 5% to 35%. The ceramic phase content in the blend is high, the fluidity is good, and the shell 100 with excellent ceramic texture and good mechanical property can be prepared. Further, the mass content of the ceramic composite material in the blend is 70% -85%, the mass content of the second ceramic particles is 7.5% -22.5%, and the mass content of the thermoplastic resin is 7.5% -22.5%. Further, the mass content of the ceramic composite material in the blend is 75% -82%, the mass content of the second ceramic particles is 8% -13%, and the mass content of the thermoplastic resin is 9% -12%. In another embodiment of the present application, an adjuvant is also included in the blend. Specifically, the auxiliary agent can be, but is not limited to, a leveling agent, a cosolvent, an antioxidant, and the like. In this application, the mixing of the various materials in the blend and the subsequent preparation of the injection molding feed are facilitated by the addition of an auxiliary agent. Specifically, the mass content of the auxiliary agent can be 0.1% -1%, 0.3% -0.8% or 0.4% -0.7% of the total mass of the ceramic composite material and the second ceramic particles. In another embodiment of the present application, a colorant is also included in the blend. By adding a colorant to the blend, it is advantageous to prepare shells 100 of different colors. Specifically, the colorant may be, but is not limited to, at least one selected from the group consisting of iron oxide, cobalt oxide, cerium oxide, nickel oxide, bismuth oxide, zinc oxide, manganese oxide, chromium oxide, copper oxide, vanadium oxide, and tin oxide, respectively; the mass content of the colorant can be 0.1% -15%, 0.3% -12% or 1% -10% of the total mass of the ceramic composite material and the second ceramic particles, etc.

In embodiments of the present application, blending includes milling by dry or wet methods, such as ball milling. In one embodiment, blending is performed by dry method, which is advantageous for improving blending efficiency. In one embodiment, the ceramic composite, the second ceramic particles, the thermoplastic resin, and the ball mill beads are placed together in a dry ball mill for 2 hours to 10 hours to obtain a blend.

In an embodiment of the present application, sanding the second ceramic particles to obtain the desired morphology, particle size, is also included prior to blending. In the embodiment of the application, the sanding rotational speed is 500r/min-2000r/min, the particle size of the sanding beads is 0.3mm-10mm, and the sanding time is 2h-16h, so that the morphology and the particle size of the second ceramic particle precursor can be improved. Further, the sanding rotational speed is 800r/min-1700r/min, the particle size of the sand beads is 1mm-8mm, and the sanding time is 4h-12h. In one embodiment, the second ceramic particles are mixed with the sanding beads for sanding. In another embodiment, the second ceramic particles, the dispersant and the sanding beads are placed in a solvent and sanded, and dried after sanding. Wherein the dispersing agent can be at least one of sodium dodecyl sulfonate, sodium hexametaphosphate, sodium benzoate and polyvinyl alcohol, and the solvent can be water, alcohol solvent or alcohol-water solvent. Further, the second ceramic particles are obtained by flash evaporation. Specifically, the flash vaporization temperature may be, but is not limited to, 100℃to 280℃and the flash vaporization rate is 2kg/h to 5kg/h. In one embodiment, by the above-described sanding treatment, second ceramic particles having a particle diameter D50 of 80nm to 5 μm can be obtained.

In S204, the blend is subjected to banburying granulation to form injection molding feeding, so that the preparation of a resin ceramic green body is facilitated. In the application, the formed injection molding feed has good fluidity, and the prepared resin ceramic green body has excellent mechanical properties.

In the present application, banburying granulation is advantageous in the injection molding process, and for example, the blend may be placed in a banburying granulation integrated machine for banburying granulation. In embodiments of the present application, the temperature of the banburying granulation is above the melting point of the resin phase in the blend and below the decomposition temperature of the resin phase in the blend. It is understood that the resin phase includes thermoplastic resins and aqueous resins. Specifically, the temperature of the banburying granulation can be, but not limited to, 150-350 ℃, 180-320 ℃, 310 ℃ or the like, and the time of the banburying granulation can be, but not limited to, 30-300 min, 60-240 min, 90-180 min or the like. Further, the banburying process is in a negative pressure state, the absolute value of the pressure is less than 0.01MPa, or the banburying process is carried out in inert gas, so that the resin phase in the blend is effectively prevented from being oxidized, and the removal of gas generated by side reaction can be effectively promoted.

In embodiments of the present application, the melt index of the injection molding feed is greater than 6g/min at 340℃and 5 kg. That is, the injection molding feed dripped in more than 6g in 1min at 340℃under 5kg load. By adopting the ceramic microspheres 10 to be matched with the second ceramic particles and the thermoplastic resin, the excellent fluidity of injection molding feeding is ensured while the ceramic phase content is increased, and the molding of the shell 100 and the improvement of performance are facilitated. Further, the melt index of the injection molding feed is greater than 10g/min. Further, the melt index of the injection molding feed is greater than 13g/min. Specifically, the melt index of the injection molding feed may be, but is not limited to, 8g/min, 12g/min, 15g/min, 17g/min, 18g/min, 25g/min, 30g/min, etc.

In this application, the process parameters of injection molding may be selected based on the nature of the resin phase in the injection molding feed. In one embodiment, the injection molding temperature is 150-350 ℃, the injection molding speed is 50-98%, and the injection pressure is 80-160 MPa. In one embodiment, when polyphenylene sulfide is selected for the thermoplastic resin, the injection molding temperature may be 290℃to 330 ℃. The shape of the resin ceramic blank obtained by injection molding can be selected, and the thickness of the resin ceramic blank can be selected according to the needs, and meanwhile, the thickness in the follow-up pressing and processing processes can be reduced, so that the thickness can be increased during injection molding. It will be appreciated that other molding methods such as casting may be used to prepare the resin ceramic body. In the application, the injection molding method is simpler to operate, and compared with casting molding, the preparation cost is low without considering the problem of compatibility between the solvent and the resin phase.

In S205, the compactness of the interior is improved by pressing the resin ceramic blank, and at the same time, the ceramic microspheres 10 are broken in the process, so that the first ceramic particles 12 are prevented from agglomerating together, and the gaps generated by the breakage are filled with the thermoplastic resin; after heat treatment, the thermoplastic resin and the aqueous resin and/or the aqueous prepolymer are crosslinked, so that the interface between the ceramic phase and the resin phase is enhanced, and the strength of the resin ceramic layer 20 is improved.

In an embodiment of the present application, pressing includes subjecting the resin ceramic body to warm isostatic pressing. The porosity in the resin ceramic blank is reduced through temperature isostatic pressing, the internal binding force is improved, and meanwhile, the ceramic microspheres 10 are broken, so that the follow-up preparation process is facilitated. The isostatic pressing technique is a technique of molding a product in a sealed high-pressure container under an ultrahigh pressure state with equal directions. Isostatic pressing technology is divided into three different types of cold isostatic pressing, warm isostatic pressing and hot isostatic pressing according to the temperature during forming and consolidation. In the application, the temperature of the temperature isostatic pressing is higher than the glass transition temperature of the resin phase in the resin ceramic blank, so that the resin phase in the resin ceramic blank can be softened, and the compactness is better under the action of pressure, so that the air holes in the resin ceramic blank are eliminated, and the binding force between the ceramic phase and the resin phase is improved; at the same time, the ceramic microspheres 10 break under the pressure force, so that the first ceramic particles 12 are prevented from agglomerating together, and subsequent processing is facilitated. It will be appreciated that other methods of lamination may also be selected.

In the embodiment of the application, the pressure of the warm isostatic pressing is 150-500 MPa, so that the ceramic microspheres 10 are broken, meanwhile, the resin ceramic blank is compacted, the process has low equipment requirements, the safety is good, and the operation and the application in practice are facilitated. Further, the pressure of the temperature isostatic pressing is 180MPa to 450MPa, 200MPa to 400MPa or 220MPa to 380MPa. In the present application, the time of warm isostatic pressing may be selected according to the thickness of the resin ceramic body. In one embodiment, the temperature of the warm isostatic pressing is 80-200 ℃, the time of the warm isostatic pressing is 0.5-2 h, and the pressure of the warm isostatic pressing is 150-500 MPa, so that the ceramic microspheres 10 can be further broken, the dispersing uniformity of the first ceramic particles 12 is improved, the porosity of the resin ceramic blank is reduced, and the internal binding force is improved. In one embodiment, the resin ceramic body may be packed into a jacket, the gas adsorbed on the surface and inside voids of the body and in the jacket may be removed, and the vacuum sealed and placed in a pressure vessel with a heating furnace for warm isostatic pressing.

In the present application, the degree of crosslinking of the resin phase is increased by heat treatment to form a stronger network structure, which increases the toughness of the resin ceramic layer 20; meanwhile, the aqueous resin and/or the aqueous prepolymer may react with and intertwine with the thermoplastic resin to form a tighter bonding interface, improving the strength of the resin ceramic layer 20. In the present application, the heat treatment temperature is determined according to the properties of the resin phase; for example, the heat treatment temperature is greater than the melting temperature of the resin phase and less than the decomposition temperature of the resin phase. In one embodiment, the temperature of the heat treatment is between 100 ℃ and 350 ℃ and the time of the heat treatment is between 6 hours and 36 hours. Further, the temperature of the heat treatment is 150-310 ℃, and the time of the heat treatment is 10-30 h. In one embodiment, when the thermoplastic resin is polyphenylene sulfide, the heat treatment may be performed at a temperature of 100 to 350 ℃ for a time of 6 to 36 hours; specifically, it may be, but is not limited to, treatment at 310℃for 24 hours.

Referring to fig. 9, a schematic process diagram of S205 in an embodiment of the present application is provided, wherein after ceramic microspheres 10 and thermoplastic resin are mixed, in a pressing process, ceramic microspheres 10 with large particle sizes are broken, meanwhile, the thermoplastic resin is in a flow state by the pressing process, and the thermoplastic resin is filled into a gap generated by the break under the action of pressure to form a ductile interface, so that the interface strength between a ceramic phase and a resin phase is improved, and the overall strength is improved; in the heat treatment process, the thermoplastic resin can undergo a chain extension reaction to form a continuous phase, so that the overall toughness is improved, and meanwhile, the thermoplastic resin and the binder undergo a reaction and are mutually fused to form a tighter bonding interface, so that the overall strength is further improved.

In the embodiment of the present application, the manufacturing method of the housing 100 further includes spraying or evaporating a protective material on the surface of the resin ceramic layer 20 to form the protective layer 30. In an embodiment, an anti-fingerprint layer is formed by evaporating an anti-fingerprint material on the surface of the resin ceramic layer 20, so as to improve the anti-fingerprint effect of the housing 100.

In an embodiment of the present application, the method for manufacturing the housing 100 further includes performing computer numerical control precision machining (CNC machining) on the housing 100. The final desired assembled fit size of the housing 100 is obtained by CNC machining. For example, the housing 100 is made flatter by CNC machining. In another embodiment of the present application, the method for manufacturing the housing 100 further includes polishing the housing 100. The surface of the shell 100 is polished and ground, so that the roughness of the surface of the shell 100 is reduced, and the ceramic texture and hardness of the surface of the shell 100 are improved. In one embodiment, the surface roughness of the housing 100 is less than 0.1 μm. By providing the housing 100 with small surface roughness, the surface glossiness and ceramic texture of the housing are enhanced, and the visual effect is improved. Further, the surface roughness of the case 100 is 0.02 μm to 0.08 μm.

The present application also provides an electronic device 200 comprising the housing 100 of any of the above embodiments. It is understood that the electronic device 200 may be, but is not limited to, a cell phone, tablet, notebook, watch, MP3, MP4, GPS navigator, digital camera, etc. Referring to fig. 10, a schematic structural diagram of an electronic device according to an embodiment of the present application is provided, where an electronic device 200 includes a housing 100. The housing 100 can improve the mechanical properties of the electronic device 200, and the electronic device 200 has a ceramic-textured appearance and excellent product competitiveness.

The preparation method of the shell and the performance of the prepared shell are further described below through specific examples and comparative examples.

Example 1a

A method of preparing a ceramic composite comprising:

adding the single-component aqueous acrylic resin into pure water at room temperature for dispersion and dissolution to obtain an aqueous acrylic resin solution, wherein the mass content of the aqueous acrylic resin in the aqueous acrylic resin solution is 3wt%; adding sodium succinate diester sulfonate, ammonium persulfate and zirconia into the aqueous acrylic resin solution at the rotating speed of 200r/min to form a mixed solution, wherein the mass content of the zirconia in the mixed solution is 50%, the mass of the sodium succinate diester sulfonate accounts for 1% of the mass of the zirconia, and the mass of the ammonium persulfate accounts for 1.5% of the mass of the sodium succinate diester sulfonate; and (3) placing the mixed solution into a sand mill to sand for 5 cycles, wherein the sand milling speed is 800r/min, and the sand milling cycle time is 20min, so as to obtain the mixed slurry.

And (3) placing the mixed slurry into a spray granulator, and performing spray circulation drying granulation at 160 ℃ to obtain the ceramic composite material, wherein the ceramic composite material comprises a plurality of ceramic microspheres, and the mass content of zirconia in the ceramic microspheres is about 93.5wt%.

Example 1b

A preparation method of a ceramic composite material is substantially the same as the preparation process of the embodiment 1a, except that zirconia in the embodiment 1a is replaced with alumina, and the obtained ceramic composite material comprises a plurality of ceramic microspheres, wherein the mass content of the alumina in the ceramic microspheres is about 93.5wt%.

Example 1c

A preparation method of a ceramic composite material is substantially the same as the preparation process of the embodiment 1a, except that the zirconia in the embodiment 1a is replaced with titania, and the obtained ceramic composite material comprises a plurality of ceramic microspheres, wherein the mass content of the titania in the ceramic microspheres is about 93.5wt%.

Example 1d

A preparation method of a ceramic composite material is substantially the same as the preparation process of the embodiment 1a, except that zirconia in the embodiment 1a is replaced with silica, and the obtained ceramic composite material comprises a plurality of ceramic microspheres, wherein the mass content of the silica in the ceramic microspheres is about 93.5wt%.

Example 2

A method for preparing a shell comprises the steps of blending 80wt% of the ceramic composite material prepared in the embodiment 1a, 10wt% of zirconia and 10wt% of polyphenylene sulfide (PPS), and carrying out banburying granulation, injection molding and pressing to prepare the shell.

Example 3

A preparation method of a shell comprises the steps of blending 80wt% of the ceramic composite material prepared in the embodiment 1b, 10wt% of alumina and 10wt% of PPS, and carrying out banburying granulation, injection molding and pressing to prepare the shell.

Example 4

A preparation method of a shell comprises the steps of blending 80wt% of the ceramic composite material prepared in the embodiment 1c, 10wt% of titanium oxide and 10wt% of PPS, and carrying out banburying granulation, injection molding and pressing to prepare the shell.

Example 5

A preparation method of a shell comprises the steps of blending 80wt% of the ceramic composite material prepared in the embodiment 1d, 10wt% of silicon oxide and 10wt% of PPS, and carrying out banburying granulation, injection molding and pressing to prepare the shell.

Example 6

A shell was prepared in much the same manner as in example 2, except that 60wt% of the ceramic composite material prepared in example 1a, 20wt% of zirconia and 20wt% of PPS were used to prepare the shell.

Example 7

A method of producing a housing was substantially the same as in example 2, except that 90wt% of the ceramic composite material produced in example 1a, 5wt% of zirconia, and 5wt% of PPS were used to produce the housing.

Example 8

A shell was prepared in much the same manner as in example 3, except that 90wt% of the ceramic composite material prepared in example 1b, 5wt% of alumina and 5wt% of PPS were used to prepare the shell.

Example 9

A method of producing a housing was substantially the same as in example 4, except that 70wt% of the ceramic composite material produced in example 1c, 15wt% of titanium oxide and 15wt% of PPS were used to produce the housing.

Example 10

A shell was prepared in much the same manner as in example 5, except that 70wt% of the ceramic composite material prepared in example 1d, 15wt% of silicon oxide and 15wt% of PPS were used to prepare the shell.

Comparative example 1

A zirconia ceramic shell is formed by sintering a zirconia ceramic blank.

Comparative example 2

Much as in example 2, except that 80wt% zirconia and 20wt% pps were blended, and subjected to banburying granulation and injection molding, a complete structure could not be formed, and a housing could not be produced.

Performance detection

The pencil hardness of the surfaces of the casings provided in the above examples and comparative examples was examined using GB/T6739-1996; providing the shells in the embodiment and the comparative example, wherein the shells are the same in size, 150mm in length, 73mm in width and 0.8mm in thickness, respectively supporting the shells on a jig (3 mm supports on four sides and suspended in the middle), freely falling from a certain height to the surface to be tested by using a stainless steel ball of 32g, measuring five points at four corners and the center of the shell for 5 times until the shells are broken, and recording the falling ball height at the moment; the glossiness of the surfaces of the shells provided by the examples and the comparative examples is detected, and the glossiness meter angles are 20 degrees, 60 degrees and 80 degrees; melt index of injection molding feed was measured during the preparation of the housing provided in the above example, and the measurement of the melt index was performed at 340℃under a load of 5kg, and the measurement results are shown in Table 1.

TABLE 1 Performance test results

The embodiments 1a-1d can be used for preparing the ceramic composite material with the ultrahigh ceramic phase content, and can be used for preparing ceramic parts, so that the mechanical properties and ceramic texture of the ceramic parts are improved. The injection molding feed in the embodiments 2-10 has high melt index, good fluidity, and can improve the mechanical property of the shell, and meanwhile, when the alumina and the PPS in the reference 2 are mixed, the zirconia content is high, so that the fluidity of the injection molding feed is poor, and the shell cannot be obtained by injection molding. The ceramic phase content in the shells prepared in examples 2-10 of the application is about 84%, the performance of the shells is similar to that of the shells prepared in comparative example 1, and the shells prepared in examples 2-10 of the application are lighter in weight and more in line with the development requirements of light and thin. The pencil hardness and the glossiness of the shells prepared in examples 2-6 and 9-10 are similar to those of the shell prepared in comparative example 1, and the ball falling height of the shell prepared by the method is superior to that of the shell prepared in comparative example 1; that is, the surface hardness and ceramic texture of the shell produced by the present application are close to those of a ceramic shell, and also have excellent toughness. In conclusion, compared with the comparative example, the shell provided by the application has excellent comprehensive performance and is beneficial to the application.

The foregoing has outlined rather broadly the more detailed description of the embodiments of the present application and the principles and embodiments of the present application, but the above description is provided merely to facilitate the understanding of the method of the present application and the core ideas thereof; also, as will occur to those of ordinary skill in the art, many modifications are possible in view of the teachings of the present application, both in the detailed description and the scope of its applications. In view of the foregoing, this description should not be construed as limiting the application.

Claims

1. The shell is characterized by comprising a resin ceramic layer, wherein the resin ceramic layer comprises a plurality of first ceramic particles, a plurality of second ceramic particles, thermoplastic resin and aqueous resin, the first ceramic particles and the second ceramic particles are dispersed in a network structure formed by crosslinking the thermoplastic resin and the aqueous resin, the resin ceramic layer is prepared from ceramic microspheres, the thermoplastic resin and the second ceramic particles, the ceramic microspheres comprise an aqueous resin layer and a plurality of first ceramic particles, the aqueous resin layer wraps the plurality of first ceramic particles, the mass content of the first ceramic particles in the ceramic microspheres is more than 92%, and the aqueous resin layer is formed by crosslinking at least one of the aqueous resin and the aqueous prepolymer under the action of an aqueous initiator and a reactive surfactant.

2. The housing of claim 1, wherein the resin ceramic layer has a total mass content of the first ceramic particles and the second ceramic particles of greater than or equal to 84%.

3. The housing of claim 1, wherein the aqueous resin and the thermoplastic resin crosslink to form the network after the ceramic microspheres are ruptured, and the first ceramic particles and the second ceramic particles are dispersed in the network to form the resin ceramic layer.

4. The housing of claim 1, wherein the thermoplastic resin comprises at least one of polyphenylene sulfide, polycarbonate, polyamide, polybutylene terephthalate, and polymethyl methacrylate, and the aqueous resin comprises at least one of an aqueous acrylic resin, an aqueous polyurethane resin, and an aqueous epoxy resin;

the first ceramic particles comprise Al ₂ O ₃ 、ZrO ₂ 、Si ₃ N ₄ 、SiO ₂ 、TiO ₂ At least one of AlN, siC and Si, wherein the particle size D50 of the first ceramic particles is 80nm-5 mu m;

the second ceramic particles comprise Al ₂ O ₃ 、ZrO ₂ 、Si ₃ N ₄ 、SiO ₂ 、TiO ₂ At least one of AlN, siC and Si, and the particle diameter D50 of the second ceramic particles is 80nm-5 mu m.

5. An electronic device comprising the housing of any one of claims 1-4.

6. A method of manufacturing a shell according to any one of claims 1 to 4, comprising:

mixing and sanding the first ceramic particles, an aqueous initiator, a reactive surfactant and a binder to obtain mixed slurry, wherein the binder comprises at least one of aqueous resin and aqueous prepolymer;

the mixed slurry is subjected to spray granulation to obtain a ceramic composite material, wherein the ceramic composite material comprises a plurality of ceramic microspheres, and the mass content of the first ceramic particles in the ceramic microspheres is more than 92%;

blending the ceramic composite, the second ceramic particles, and a thermoplastic resin to form a blend;

the blend is subjected to banburying granulation to form injection molding feeding, and the injection molding feeding is subjected to injection molding to obtain a resin ceramic blank;

and pressing and heat treating the resin ceramic blank to obtain a resin ceramic layer, and thus obtaining the shell.

7. The method of claim 6, wherein the blend comprises 60% to 90% by mass of the ceramic composite material, 5% to 33% by mass of the second ceramic particles, and 5% to 35% by mass of the thermoplastic resin.

8. The method of manufacturing according to claim 6, wherein the mass ratio of the ceramic composite material to the second ceramic particles in the blend is 1.7-18.

9. The method of manufacturing according to claim 6, wherein the resin ceramic body is pressed and heat-treated to obtain the resin ceramic layer, comprising: carrying out temperature isostatic pressing on the resin ceramic blank, wherein the temperature of the temperature isostatic pressing is 80-200 ℃, the temperature of the temperature isostatic pressing is higher than the glass transition temperature of the thermoplastic resin, the pressure of the temperature isostatic pressing is 150-500 MPa, and the time of the temperature isostatic pressing is 0.5-2 h; the temperature of the heat treatment is 100-350 ℃, and the time of the heat treatment is 6-36 h.